KR20230052507A - organic compounds containing 2-cyanoethyl group and preparing method thereof - Google Patents
organic compounds containing 2-cyanoethyl group and preparing method thereof Download PDFInfo
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- KR20230052507A KR20230052507A KR1020210135640A KR20210135640A KR20230052507A KR 20230052507 A KR20230052507 A KR 20230052507A KR 1020210135640 A KR1020210135640 A KR 1020210135640A KR 20210135640 A KR20210135640 A KR 20210135640A KR 20230052507 A KR20230052507 A KR 20230052507A
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- organic compound
- cyanoethyl group
- compound containing
- acrylonitrile
- reaction
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- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 title claims abstract description 104
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims description 11
- 239000002904 solvent Substances 0.000 claims abstract description 40
- 150000002576 ketones Chemical class 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 92
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 40
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000005453 ketone based solvent Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 11
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 6
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 6
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 238000007086 side reaction Methods 0.000 abstract description 22
- 238000000746 purification Methods 0.000 abstract description 17
- 238000007711 solidification Methods 0.000 abstract description 5
- 230000008023 solidification Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000004904 shortening Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 31
- 239000012044 organic layer Substances 0.000 description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 239000012153 distilled water Substances 0.000 description 22
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- 238000006467 substitution reaction Methods 0.000 description 18
- 239000006227 byproduct Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 14
- 238000005191 phase separation Methods 0.000 description 14
- 238000007278 cyanoethylation reaction Methods 0.000 description 11
- 239000000376 reactant Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000012467 final product Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NTFJXDRAVMOYBG-UHFFFAOYSA-N 2-(2,2-dicyanoethoxymethyl)propanedinitrile Chemical compound N#CC(C#N)COCC(C#N)C#N NTFJXDRAVMOYBG-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004373 Pullulan Substances 0.000 description 3
- 229920001218 Pullulan Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000005575 aldol reaction Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 235000019423 pullulan Nutrition 0.000 description 3
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- QSCYEVCZRKTLKP-UHFFFAOYSA-N propan-2-one;prop-2-enenitrile Chemical compound CC(C)=O.C=CC#N QSCYEVCZRKTLKP-UHFFFAOYSA-N 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000007696 Kjeldahl method Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JXBPSENIJJPTCI-UHFFFAOYSA-N ethyl cyanate Chemical group CCOC#N JXBPSENIJJPTCI-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
- C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
본 발명은 2-시아노에틸기를 포함하는 유기화합물 및 이의 제조방법에 관한 것으로, 더욱 상세하게는 반응물의 부반응을 억제하여 짧은 시간에 높은 치환율을 가지는 고순도의 2-시아노에틸기를 포함하는 유기화합물 및 이의 제조방법에 관한 것이다.The present invention relates to an organic compound containing a 2-cyanoethyl group and a method for producing the same, and more particularly, to an organic compound containing a high-purity 2-cyanoethyl group having a high substitution rate in a short time by suppressing side reactions of reactants And it relates to a manufacturing method thereof.
2-시아노에틸기를 포함하는 유기화합물은 2-시아노에틸기의 높은 편극화로 인해 다른 유기화합물에 비해 유전상수가 높으므로 유기 EL 소자를 비롯한 다양한 분야에서 사용되어 왔다. 또한, 최근에는 리튬이차전지의 내열성 및 열적안정성을 강화하기 위해 세라믹 분리막의 바인더 첨가제로 사용되고 있다.An organic compound containing a 2-cyanoethyl group has a higher dielectric constant than other organic compounds due to the high polarization of the 2-cyanoethyl group, and thus has been used in various fields including organic EL devices. In addition, recently, it is used as a binder additive for ceramic separators to enhance heat resistance and thermal stability of lithium secondary batteries.
이러한 2-시아노에틸기를 포함하는 유기화합물은 일반적으로 수산기를 포함하는 유기화합물과 아크릴로니트릴을 촉매 존재 하에 마이클 부가 반응에 의해서 제조할 수 있다. 하지만 원활한 반응을 위해서는 수산기를 포함하는 유기화합물에 비해 과량의 아크릴로니트릴이 필요하며, 이러한 과량의 아크릴로니트릴은 반응 후 미반응 상태로 남아있거나 부반응으로 인해 다양한 부산물이 형성된다. 따라서 이를 제거하기 위해서는 용매에 용해 후 물을 비롯한 비용매에 침전시켜 미반응 아크릴로니트릴 및 이로부터 발생하는 부산물을 정제하는 과정을 수 번 반복해야 한다. 또한 정제 후에도 소량의 부산물이 존재할 수 있으며, 이러한 정제과정에서 다량의 악성 폐수가 발생하게 되어 높은 처리비용이 소요되고 있는 실정이다.Such an organic compound containing a 2-cyanoethyl group can generally be prepared by a Michael addition reaction between an organic compound containing a hydroxyl group and acrylonitrile in the presence of a catalyst. However, for a smooth reaction, an excess of acrylonitrile is required compared to the organic compound containing a hydroxyl group, and such excess acrylonitrile remains unreacted after the reaction or various by-products are formed due to side reactions. Therefore, in order to remove it, it is necessary to repeat the process of purifying unreacted acrylonitrile and by-products generated therefrom by precipitating in non-solvents including water after dissolving in a solvent several times. In addition, a small amount of by-products may exist even after purification, and a large amount of malignant wastewater is generated during the purification process, which requires high treatment costs.
이와 관련하여, 한국등록특허 제1730671호는 수산기를 갖는 중합체를 물에 녹인 후 촉매와 혼합 및 정제과정에서 온수를 사용하여 용해도를 높여 최종생성물에 포함된 부산물인 비스-시아노에틸에테르의 함량을 줄일 수 있음을 개시하고 있다. 또한, 한국공개특허 제2020-0011016호, 한국공개특허 제2020-0033672호는 2-시아노에틸기 함유 중합체 및 아세톤에 대한 특정 한센 용해도 파라미터 거리를 가지는 추출 용매를 사용하여 비스-시아노에틸에테르를 제거하여 폐수 발생량을 줄일 수 있는 방법에 대해 개시하고 있다.In this regard, Korean Patent Registration No. 1730671 discloses that after dissolving a polymer having a hydroxyl group in water, the content of bis-cyanoethyl ether, a by-product included in the final product, is increased by using hot water in the process of mixing and refining with a catalyst to increase solubility. It shows that it can be reduced. In addition, Korean Patent Publication No. 2020-0011016 and Korean Patent Publication No. 2020-0033672 disclose bis-cyanoethyl ether using an extraction solvent having a specific Hansen solubility parameter distance for a 2-cyanoethyl group-containing polymer and acetone. It discloses a method to reduce the amount of wastewater by removing it.
그러나, 이러한 종래기술들의 다양한 기술적 제안에도 불구하고, 정제과정에서 부산물을 제거하거나 특정 부산물 생성만을 저하시킬 뿐 본질적 문제인 반응물의 부반응을 억제하는 기술까지는 도달하지 못하고 있다.However, despite various technical proposals of these prior arts, technology for suppressing side reactions of reactants, which is an essential problem, has not been reached, only removing by-products or reducing the production of specific by-products in the purification process.
한편, 2-시아노에틸기를 포함하는 유기화합물을 제조하는 과정에서 발생할 수 있는 불량으로는 대표적으로 유기층이 상부의 액체상태로 존재하지 않고 수층 내에서 고형이 발생하는 현상이 있지만 이를 해결하기 위한 과제는 소홀히 연구되어 왔다. 또한, 2-시아노에틸기를 포함하는 유기화합물을 제조함에 있어서 상기 반응물의 부반응 뿐만 아니라 반응에 참여하여 용매에 대한 부반응이 발생할 수도 있다는 사실에 대해서는 간과된 측면이 있었다. 이 경우에 발생하는 부반응 물질도 최종 제품의 물성에 부정적인 영향을 줄 수 있는데, 이에 대한 해결방법에 대해서는 아직 연구가 없는 실정이다.On the other hand, defects that may occur in the process of manufacturing an organic compound containing a 2-cyanoethyl group include a phenomenon in which the organic layer does not exist in a liquid state at the top and a solid occurs in the water layer. has been neglected. In addition, in preparing an organic compound containing a 2-cyanoethyl group, there was an overlooked aspect of the fact that not only side reactions of the reactants but also side reactions to solvents may occur by participating in the reaction. Side reaction substances generated in this case may also have a negative effect on the physical properties of the final product, but there is no research on a solution to this problem yet.
따라서, 본 발명은 2-시아노에틸기를 포함하는 유기화합물을 제조함에 있어서 발생할 수 있는 고형화 불량을 방지하고 사용하는 케톤류 용매의 부반응을 억제하여 고순도의 2-시아노에틸기를 포함하는 유기화합물 및 이의 제조방법을 제공하는 것을 목적으로 한다.Therefore, the present invention provides a high-purity organic compound containing a 2-cyanoethyl group and its It is an object of the present invention to provide a manufacturing method.
상기 문제를 해결하기 위하여,In order to solve the above problem,
본 발명의 일 구현예는 수산기 함유 유기화합물, 아크릴로니트릴, 염기성 촉매 및 케톤류 용매의 반응으로 형성되는 2-시아노에틸기를 포함하는 유기화합물의 제조방법으로서,One embodiment of the present invention is a method for producing an organic compound containing a 2-cyanoethyl group formed by the reaction of a hydroxyl group-containing organic compound, acrylonitrile, a basic catalyst and a ketone solvent,
상기 반응 과정에 있어서 2-시아노에틸기를 포함하는 유기화합물에 대한 아크릴로니트릴의 중량 및 케톤류 용매의 중량과 상기 유기화합물에 대한 상기 아크릴로니트릴 및 케톤류 용매의 용해도의 관계가 하기의 수학식 1을 만족하도록 반응조건을 설정하는 것인, 2-시아노에틸기를 포함하는 유기화합물의 제조방법을 제공한다:In the reaction process, the relationship between the weight of acrylonitrile and the weight of ketone solvents for the organic compound containing a 2-cyanoethyl group and the solubility of the acrylonitrile and ketone solvents for the organic compound is expressed by Equation 1 below: Provided is a method for producing an organic compound containing a 2-cyanoethyl group, wherein the reaction conditions are set to satisfy:
(상기 수학식 1 및 수학식 2에서 Wa는 반응동안 생성된 2-시아노에틸기를 포함하는 유기화합물의 중량이고, Wb는 아크릴로니트릴의 중량이며, Wc는 케톤류 용매의 중량이다. 또한, 상기 수학식 1에서 Sb는 아크릴로니트릴에 대한 2-시아노에틸기를 포함하는 유기화합물의 용해도이고, Sc는 케톤류 용매에 대한 시아노에틸기를 포함하는 유기화합물의 용해도이다).(In Equations 1 and 2, Wa is the weight of an organic compound containing a 2-cyanoethyl group generated during the reaction, Wb is the weight of acrylonitrile, and Wc is the weight of a ketone solvent. In addition, the above In Equation 1, Sb is the solubility of an organic compound containing a 2-cyanoethyl group in acrylonitrile, and Sc is the solubility of an organic compound containing a cyanoethyl group in ketone solvents).
상기 구현예에서, 상기 수산기 함유 유기화합물에는 폴리비닐알코올이 포함되는 고분자, 또는 풀루란, 셀룰로오스, 히드록시알킬셀룰로오스, 글리세롤이 포함되는 다당류 화합물 또는 이들의 유도체 화합물이 포함될 수 있다.In the above embodiment, the hydroxyl group-containing organic compound may include a polymer including polyvinyl alcohol, or a polysaccharide compound including pullulan, cellulose, hydroxyalkyl cellulose, and glycerol, or derivative compounds thereof.
또한 상기 구현예에서, 상기 염기성 촉매에는 알칼리금속 수산화물, 알칼리토금속 수산화물, 알칼리금속 탄산염, 알칼리토금속 탄산염, 암모니아수 및 이들의 혼합물이 포함될 수 있다. Also, in the above embodiment, the basic catalyst may include an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, an alkaline earth metal carbonate, ammonia water, and a mixture thereof.
아울러, 상기 케톤류 용매에는 아세톤이 포함될 수 있다.In addition, acetone may be included in the ketone solvent.
그리고, 상기 구현예에 있어서, 상기 수산기 함유 유기화합물에는 폴리비닐알코올이 포함될 수 있다.And, in the above embodiment, polyvinyl alcohol may be included in the hydroxyl group-containing organic compound.
한편 본 발명의 다른 구현예는 수산기 함유 유기화합물, 아크릴로니트릴, 염기성 촉매 및 케톤류 용매의 반응으로 형성되는 2-시아노에틸기를 포함하는 유기화합물에 있어서, 상기 2-시아노에틸기를 포함하는 유기화합물 내에 하기 화학식 1로 표시되는 화합물과 하기 화학식 2로 표시되는 화합물의 총량이 상기 2-시아노에틸기를 포함하는 유기화합물 전체 대비 0.2wt% 이하인 것인, 2-시아노에틸기를 포함하는 유기화합물을 제공한다:On the other hand, another embodiment of the present invention is an organic compound containing a 2-cyanoethyl group formed by the reaction of a hydroxyl group-containing organic compound, acrylonitrile, a basic catalyst, and a ketone solvent, wherein the organic compound containing the 2-cyanoethyl group An organic compound containing a 2-cyanoethyl group, wherein the total amount of the compound represented by Formula 1 and the compound represented by Formula 2 in the compound is 0.2 wt% or less relative to the total amount of the organic compound containing the 2-cyanoethyl group provides:
(상기 화학식 1에서 R1, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1~5개의 알킬기이다), 및(In Formula 1, R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms), and
(상기 화학식 2에서 상기 화학식 1에서 R1, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1~5개의 알킬기이다).(In Formula 2, R 1 , R 2 and R 3 in Formula 1 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms).
상기 다른 구현예에서, 상기 수산기 함유 유기화합물에는 폴리비닐알코올이 포함되는 고분자, 또는 풀루란, 셀룰로오스, 히드록시알킬셀룰로오스, 글리세롤이 포함되는 다당류 화합물 또는 이들의 유도체 화합물이 포함될 수 있다.In the other embodiment, the hydroxyl group-containing organic compound may include a polymer including polyvinyl alcohol, a polysaccharide compound including pullulan, cellulose, hydroxyalkyl cellulose, glycerol, or derivative compounds thereof.
또한, 상기 염기성 촉매에는 알칼리금속 수산화물, 알칼리토금속 수산화물, 알칼리금속 탄산염, 알칼리토금속 탄산염, 암모니아수 및 이들의 혼합물이 포함될 수 있다.In addition, the basic catalyst may include alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate, ammonia water, and mixtures thereof.
아울러, 상기 케톤류 용매에는 아세톤이 포함될 수 있고, 상기 수산기 함유 유기화합물에는 폴리비닐알코올이 포함될 수 있다.In addition, acetone may be included in the ketone solvent, and polyvinyl alcohol may be included in the hydroxyl group-containing organic compound.
본 발명에 따르면, 고순도의 2-시아노에틸기를 포함하는 유기화합물의 제조를 가능하게 하고, 고형화 불량을 방지하고 용매 부반응을 억제하여 고품질의 제품을 제공할 수 있다. 또한 정제과정을 단축시켜 폐수 발생량을 감소시킬 수 있다.According to the present invention, it is possible to produce a high-purity organic compound containing a 2-cyanoethyl group, prevent solidification defects, and suppress side reactions of a solvent, thereby providing a high-quality product. In addition, by shortening the purification process, the amount of wastewater generated can be reduced.
이하에 본 발명을 상세하게 설명하기에 앞서, 본 명세서에 사용된 용어는 특정의 실시예를 기술하기 위한 것일 뿐 본 발명의 범위를 한정하려는 것은 아님을 이해하여야 한다. 본 명세서에 사용되는 모든 기술용어 및 과학용어는 다른 언급이 없는 한은 기술적으로 통상의 기술을 가진 자에게 일반적으로 이해되는 것과 동일한 의미를 가진다.Prior to describing the present invention in detail below, it should be understood that terms used herein are intended to describe specific embodiments and are not intended to limit the scope of the present invention. All technical and scientific terms used herein have the same meaning as commonly understood by a person of ordinary skill in the art unless otherwise specified.
본 명세서 및 청구범위의 전반에 걸쳐, 다른 언급이 없는 한 포함(comprise, comprises, comprising)이라는 용어는 언급된 물건, 단계 또는 일군의 물건, 및 단계를 포함하는 것을 의미하고, 임의의 어떤 다른 물건, 단계 또는 일군의 물건 또는 일군의 단계를 배제하는 의미로 사용된 것은 아니다.Throughout this specification and claims, the terms "comprise", "comprise" and "comprising", unless stated otherwise, are meant to include a stated object, step or group of objects, and steps, and any other object However, it is not used in the sense of excluding a step or a group of objects or a group of steps.
한편, 본 발명의 여러가지 구현예 및 실시예들은 명확한 반대의 지적이 없는 한 그 외의 어떤 다른 실시예들과 결합될 수 있다. 특히, 바람직하거나 유리하다고 지시하는 어떤 특징도 바람직하거나 유리하다고 지시한 그 외의 어떤 특징들과 결합될 수 있다.On the other hand, various implementations and embodiments of the present invention can be combined with any other embodiments unless clearly indicated to the contrary. In particular, any feature indicated as being desirable or advantageous may be combined with any other feature indicated as being desirable or advantageous.
본 발명자들은 2-시아노에틸기를 포함하는 유기화합물의 제조방법에 대한 다양한 실험을 수행하고, 부산물 생성의 문제점을 해결하기 위해 노력하였다. 그 결과, 케톤류의 용매를 사용하여 반응을 진행함에 있어서, 시아노에틸화 반응동안 시아노에틸기를 포함하는 유기화합물에 대한 아크릴로니트릴 중량 및 케톤류 용매의 중량을 조절할 경우 반응 시 유기층의 역전을 방지하여 불완전 반응을 방지할 수 있고, 이에 따라 부반응을 최소화하여 최종 제품에 부정적인 영향을 미치는 부산물의 함량을 줄일 수 있다는 것을 밝혀냈다. The inventors of the present invention performed various experiments on a method for preparing an organic compound containing a 2-cyanoethyl group, and tried to solve the problem of by-product production. As a result, in the reaction using a ketone solvent, when the weight of acrylonitrile for the organic compound containing a cyanoethyl group and the weight of the ketone solvent are adjusted during the cyanoethylation reaction, inversion of the organic layer is prevented. It was found that incomplete reactions can be prevented by doing so, and side reactions can be minimized thereby reducing the content of by-products that negatively affect the final product.
2-시아노에틸기를 포함하는 유기화합물은 일반적으로 하기 [반응식 1]에 나타난 바와 같이 반응물로서 수산기를 포함하는 유기화합물 내에 존재하는 수산기와 아크릴로니트릴의 시아노에틸화(cyanoethylation) 반응으로 얻어지며, 이때 염기성 물질이 촉매로 사용된다. An organic compound containing a 2-cyanoethyl group is generally obtained by a cyanoethylation reaction of a hydroxyl group present in an organic compound containing a hydroxyl group as a reactant and acrylonitrile, as shown in [Scheme 1] below. , where a basic substance is used as a catalyst.
[반응식 1][Scheme 1]
상기 [반응식 1]에서, R-OH는 수산기를 포함하는 유기화합물, R-O-CH2CH2CN은 2-시아노에틸기를 포함하는 유기화합물을 나타낸다.In [Reaction Scheme 1], R-OH represents an organic compound containing a hydroxyl group, and RO-CH 2 CH 2 CN represents an organic compound containing a 2-cyanoethyl group.
상기 수산기를 포함하는 유기화합물은 아크릴로니트릴과 시아노에틸화 반응이 가능한 것이면 어느 유기화합물도 비제한적으로 사용할 수 있다. 예를 들면, 상기 유기화합물에는 폴리비닐알코올 등의 고분자이거나 풀루란, 셀룰로오스, 히드록시알킬셀룰로오스, 글리세롤 등의 다당류 화합물 또는 이들의 유도체 화합물이 포함될 수 있다. 상기 예시적인 유기화합물 중 폴리비닐알코올은 가격이 합리적이고 접착력 및 내열성이 강해 다양한 분야에서 사용하고 있다. 또한, 2-시아노에틸기로 치환된 폴리비닐알코올은 높은 유전상수 및 피막 형성성, 접착력을 가지기 때문에 고유전성 및 접착력을 요구하는 분야에 적합하다. 아울러, 세라믹 입자와의 상호작용으로 인해 세라믹 입자의 분산성을 높이고, 분리막 원단과의 높은 접착력을 가지므로 세라믹 분리막의 분산제 또는 바인더로 사용하기에 적합하다.As the organic compound containing the hydroxyl group, any organic compound capable of reacting with acrylonitrile and cyanoethylation may be used without limitation. For example, the organic compound may include a polymer such as polyvinyl alcohol or a polysaccharide compound such as pullulan, cellulose, hydroxyalkyl cellulose, or glycerol, or a derivative compound thereof. Among the exemplary organic compounds, polyvinyl alcohol is used in various fields because of its reasonable price and strong adhesion and heat resistance. In addition, since polyvinyl alcohol substituted with 2-cyanoethyl group has a high dielectric constant, film formation, and adhesive strength, it is suitable for fields requiring high dielectric strength and adhesive strength. In addition, due to the interaction with the ceramic particles, the dispersibility of the ceramic particles is increased, and since it has high adhesive strength with the fabric of the separator, it is suitable for use as a dispersant or binder for a ceramic separator.
상기 시아노에틸화 반응에 있어서 염기성 촉매를 사용할 수 있는데, 상기 염기성 촉매에는 알칼리금속 수산화물, 알칼리토금속 수산화물, 알칼리금속 탄산염, 알칼리토금속 탄산염, 암모니아수 및 이들의 혼합물이 포함될 수 있다. 구체적으로, 상기 알칼리금속 수산화물은 수산화 리튬, 수산화나트륨, 수산화 칼륨 등일 수 있고, 상기 알칼리금속 탄산염은 탄산나트륨, 탄산칼륨 등일 수 있다. 상기 염기성 촉매는 단독으로 사용될 수 있고, 상이동 촉매 (phase transfer catalyst)와 혼합하여 사용될 수 있다. 상기 상이동 촉매에는 테트라메틸암모늄 클로라이드, 테트라에틸암모늄 아이오다이드, 테트라부틸암모늄 브로마이드 또는 이들의 혼합물 등이 포함될 수 있다.In the cyanoethylation reaction, a basic catalyst may be used, and the basic catalyst may include an alkali metal hydroxide, an alkaline earth metal hydroxide, an alkali metal carbonate, an alkaline earth metal carbonate, ammonia water, and a mixture thereof. Specifically, the alkali metal hydroxide may be lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like, and the alkali metal carbonate may be sodium carbonate, potassium carbonate, and the like. The basic catalyst may be used alone or in combination with a phase transfer catalyst. The phase transfer catalyst may include tetramethylammonium chloride, tetraethylammonium iodide, tetrabutylammonium bromide, or a mixture thereof.
상기 시아노에틸화 반응에서 2-시아노에틸기의 치환율에 영향을 주는 요인은 수산기를 포함하는 유기화합물의 수산기에 대한 아크릴로니트릴, 염기성 촉매, 용매 및 물의 질량 비 또는 몰 비일 수 있는데, 이에 따라 수산기로부터 시아노에틸 에테르기로 치환되는 정도가 다르다. 그 중에서도 용매는 2-시아노에틸기를 포함하는 유기화합물을 생성하는 반응에 있어서 반응계를 제공하는 역할을 하는데, 반응물과의 용해도 등을 조절하여 반응물이 서로 반응에 참여할 수 있도록 한다.Factors affecting the substitution rate of 2-cyanoethyl group in the cyanoethylation reaction may be the mass ratio or molar ratio of acrylonitrile, basic catalyst, solvent and water to the hydroxyl group of an organic compound containing a hydroxyl group. The degree of substitution from hydroxyl groups to cyanoethyl ether groups is different. Among them, the solvent plays a role of providing a reaction system in the reaction to produce an organic compound containing a 2-cyanoethyl group, and allows the reactants to participate in the reaction with each other by adjusting the solubility of the reactants.
다시 말해서, 2-시아노에틸기를 함유하는 유기화합물을 제조함에 있어서 시아노에틸화반응은 수산기를 포함하는 유기화합물 내지 염기성 촉매를 포함하는 수층과 아크릴로니트릴 및 아세톤과 같은 케톤류 용매를 포함하는 유기층의 시아노에틸화반응을 통해 생성된다. 반응물이 생성물로 전환이 완료된 시점에서 유기층과 수층을 분리하는 과정을 진행하는데, 유기층이 역전되는 경우가 종종 발생한다. 이 경우 반응이 불안정하게 되어 최종적으로 원하는 순도의 2-시아노에틸기를 포함하는 유기화합물을 수득하기 어려워진다. In other words, in preparing an organic compound containing a 2-cyanoethyl group, the cyanoethylation reaction is performed by using an organic compound containing a hydroxyl group or an aqueous layer containing a basic catalyst and an organic layer containing a ketone solvent such as acrylonitrile and acetone. It is produced through the cyanoethylation reaction of When the conversion of reactants to products is completed, the process of separating the organic layer and the aqueous layer proceeds, but the organic layer is often reversed. In this case, the reaction becomes unstable, and finally, it becomes difficult to obtain an organic compound containing a 2-cyanoethyl group of desired purity.
상기 유기층과 수층이 역전되는 현상은 생성된 2-시아노에틸기를 함유하는 유기화합물의 양과 미반응 아크릴로니트릴, 케톤류 용매의 양과 밀접한 관계가 있다. 반응 종료시점을 기준으로 미반응 아크릴로니트릴과 케톤류 용매의 양이 생성된 2-시아노에틸기를 함유하는 유기화합물을 충분히 용해시킬 수 있는 양보다 적으면 2-시아노에틸기를 함유하는 유기화합물은 유기층에 용해된 상태로 존재하지 못하고 수층과의 반응에서 작은 입자를 형성하게 되고 이렇게 생성된 작은 입자들이 서로 결합하여 고형상태의 하나의 큰 침전물을 형성하게 된다. 이때 생성된 2-시아노에틸기를 함유하는 유기화합물의 침전물은 촉매, 부반응으로 생성된 아크릴산 또는 아크릴아마이드 등이 포함되어있는 수층에서 생성되며, 침전물 내부에 촉매와 부산물이 포함되게 되어 정제를 반복하더라도 충분히 제거하기가 어렵다. 본 발명자는 고순도의 2-시아노에틸기 포함 유기화합물을 수득하기 위한 연구개발 중, 유기층과 수층이 역전되거나 부산물을 다량 포함하는 이유 중의 하나가 유기층을 이루고 있는 아크릴로니트릴과 케톤류 용매의 부반응에 의한 소모에 따른 것일 수 있음을 밝혀냈다.The phenomenon in which the organic layer and the aqueous layer are reversed is closely related to the amount of the organic compound containing the 2-cyanoethyl group produced and the amount of unreacted acrylonitrile and ketone solvents. If the amount of unreacted acrylonitrile and ketone solvent based on the reaction end point is less than the amount that can sufficiently dissolve the organic compound containing the 2-cyanoethyl group produced, the organic compound containing the 2-cyanoethyl group is It does not exist in a dissolved state in the organic layer and forms small particles in the reaction with the aqueous layer, and the small particles thus formed combine with each other to form one large precipitate in a solid state. The precipitate of the organic compound containing the 2-cyanoethyl group produced at this time is produced in the water layer containing the catalyst and acrylic acid or acrylamide produced by side reactions, and the catalyst and by-products are included in the precipitate, even after repeated purification Hard enough to remove. During research and development to obtain a high-purity organic compound containing a 2-cyanoethyl group, one of the reasons why the organic layer and the aqueous layer are inverted or contain a large amount of by-products is due to the side reaction of acrylonitrile and ketone solvents constituting the organic layer. It was found that it may be due to consumption.
상기 반응식 1의 주 반응물이자 유기층의 용매역할을 하는 아크릴로니트릴은 하기 반응식 2와 같이 염기 촉매 존재 하에 가수분해(hydrolysis) 반응이 일어나 아크릴아마이드(acrylamide)가 생성되고, 생성된 아크릴아마이드는 다시 가수분해 반응으로 인해 최종적으로 아크릴산(acrylic acid)이 생성된다. 생성된 아크릴산은 분위기에 따라 아크릴산 이온 또는 아크릴산 금속 염을 형성하게 되는데 이는 사용하는 염기성 촉매의 금속 이온의 종류에 따라 달라질 수 있다. 예를 들어, 염기성 촉매로 수산화나트륨을 사용한 경우 소듐 아크릴레이트(sodium acrylate)가 형성된다. 이렇게 생성된 부산물은 수층에 용해되므로 결론적으로 2-시아노에틸기를 함유하는 유기화합물을 용해시킬 수 있는 전체 용매는 감소하게 된다.Acrylonitrile, which is the main reactant in Reaction Scheme 1 and serves as a solvent for the organic layer, undergoes a hydrolysis reaction in the presence of a base catalyst as shown in Reaction Scheme 2 to produce acrylamide, and the resulting acrylamide is hydrolyzed again. As a result of the decomposition reaction, acrylic acid is finally produced. The produced acrylic acid forms acrylic acid ions or acrylic acid metal salts depending on the atmosphere, which may vary depending on the type of metal ions of the basic catalyst used. For example, when sodium hydroxide is used as a basic catalyst, sodium acrylate is formed. Since the by-products thus produced are dissolved in the water layer, the total number of solvents capable of dissolving the organic compound containing the 2-cyanoethyl group is reduced.
[반응식 2][Scheme 2]
또한 유기층을 이루는 다른 용매인 케톤류 용매는 자체 알돌반응(aldol reaction)에 의해 소모될 수 있다. 예를 들어, 2-시아노에틸기를 포함하는 유기화합물을 제조함에 있어서 케톤류 용매의 하나인 아세톤을 용매로 사용하는 경우에 하기의 반응식 3에서 보는 바와 같이, 아세톤이 염기 촉매 하에서 자체 알돌반응을 일으키게 되어 디아세톤 알코올(4-하이드록시-4-메틸펜탄-2-온)으로 전환 후 축합되어 메시틸 옥사이드(mesithyl oxide)로 전환된다.(하기 반응식 3 참고)In addition, ketone solvents, which are other solvents constituting the organic layer, may be consumed by their own aldol reaction. For example, when acetone, one of the ketone solvents, is used as a solvent in preparing an organic compound containing a 2-cyanoethyl group, as shown in Reaction Formula 3 below, acetone causes its own aldol reaction under a base catalyst. After conversion to diacetone alcohol (4-hydroxy-4-methylpentan-2-one), it is condensed and converted to mesithyl oxide (see Scheme 3 below).
[반응식 3][Scheme 3]
상기 디아세톤 알코올은 끓는점(Boiling point)이 160℃를 상회하고, 메시틸 옥사이드 또한 끓는점이 130℃ 부근이어서 2-시아노에틸기를 포함하는 유기화합물의 정제 후 수행하는 건조공정의 온도(약 110℃ 부근)에서 휘발되지 않아 최종 제품의 물성을 저해하는 요인이 된다.The diacetone alcohol has a boiling point above 160 ° C, and mesityl oxide also has a boiling point near 130 ° C, so the temperature of the drying process (about 110 ° C. It is not volatilized in the vicinity) and becomes a factor that impairs the physical properties of the final product.
이처럼, 상기 아크릴로니트릴 및 아세톤의 부반응으로 인해 용매의 양이 감소하게 되면 생성된 2-시아노에틸기를 포함하는 유기화합물이 유기층에 충분히 용해되지 못한다. 이 때문에 상기 2-시아노에틸기를 포함하는 유기화합물이 수층에서 작은 입자로 고형화된 후 임계점에 도달하면, 유기층과 수층의 계면 평형이 깨지면서 하나로 합쳐진 벌크(bulk) 형태로 침전되는 결과를 초래할 수 있다.As such, when the amount of the solvent decreases due to the side reaction of the acrylonitrile and acetone, the organic compound containing the 2-cyanoethyl group is not sufficiently dissolved in the organic layer. For this reason, when the organic compound containing the 2-cyanoethyl group is solidified into small particles in the water layer and reaches a critical point, the interface equilibrium between the organic layer and the water layer is broken and precipitated in the form of a combined bulk. .
반응 중 용매의 양에 대한 반응계의 거동을 확인하기 위해 아크릴로니트릴 및 아세톤에 대한 2-시아노에틸기를 포함하는 유기화합물의 용해도를 시아노에틸기의 치환율에 대해 측정하였으며, 그 결과를 아래 표 1에 나타내었다. 여기서 사용한 수산기를 포함하는 유기화합물은 폴리비닐알코올 고분자를 사용하였으며, 아크릴로니트릴과 촉매, 반응시간을 조절하여 일정 치환율을 가지는 2-시아노에틸기를 포함하는 폴리비닐알코올을 얻었다. 치환율이 증가할수록 아크릴로니트릴 및 아세톤에 대한 용해도는 증가하며, 같은 치환율의 경우 아크릴로니트릴보다 아세톤에 대한 용해도가 더 높은 경향을 보이는 것을 확인하였다.In order to confirm the behavior of the reaction system with respect to the amount of solvent during the reaction, the solubility of the organic compound containing the 2-cyanoethyl group in acrylonitrile and acetone was measured for the substitution rate of the cyanoethyl group, and the results are shown in Table 1 below. shown in A polyvinyl alcohol polymer was used as the organic compound containing a hydroxyl group used here, and polyvinyl alcohol containing a 2-cyanoethyl group having a certain substitution rate was obtained by adjusting acrylonitrile, a catalyst, and a reaction time. As the substitution rate increased, the solubility in acrylonitrile and acetone increased, and it was confirmed that the solubility in acetone tended to be higher than that in acrylonitrile in the case of the same substitution rate.
상기 표에 따르면 시아노에틸기 80%몰의 치환율을 가지는 시아노에틸기를 포함하는 폴리비닐알코올 100g을 용해시키기 위해 필요한 최소 용매량은 아크릴로니트릴 단독으로 사용할 경우 280g이며, 아세톤 단독으로 사용할 경우 257g을 필요로 한다. 하지만 반응과정에서 아크릴로니트릴이 반응물로 사용되므로 실제 반응에서는 아크릴로니트릴과 아세톤의 혼합용매가 사용될 수 있다.According to the above table, the minimum amount of solvent required to dissolve 100 g of polyvinyl alcohol containing a cyanoethyl group having a substitution rate of 80% by mole of cyanoethyl group is 280 g when acrylonitrile is used alone and 257 g when acetone is used alone. in need. However, since acrylonitrile is used as a reactant in the reaction process, a mixed solvent of acrylonitrile and acetone may be used in the actual reaction.
즉, 최종적으로 아크릴로니트릴과 아세톤의 혼합용매가 생성된 2-시아노에틸기를 포함하는 유기화합물을 충분히 용해시킬 수 있는 양 이상일 때 안정적으로 반응이 가능하며, 반응 종료 후 유기층과 수층의 상분리가 일어나게 된다. That is, when the amount of the finally mixed solvent of acrylonitrile and acetone is higher than the amount capable of sufficiently dissolving the organic compound containing the generated 2-cyanoethyl group, the reaction is stably possible, and the phase separation of the organic layer and the aqueous layer is possible after the reaction is completed. It happens.
이때, 아세톤은 물에 용해되므로 명확한 상분리를 유도하기 위해서는 아크릴로니트릴과 아세톤의 비가 60:40 내지 95:5로 아크릴로니트릴의 비가 높은 것이 바람직하다. At this time, since acetone is soluble in water, it is preferable that the ratio of acrylonitrile and acetone is 60:40 to 95:5 and the ratio of acrylonitrile is high in order to induce a clear phase separation.
유기층 용매의 부반응으로 인해 생성된 2-시아노에틸기를 포함하는 유기화합물을 모두 용해시키지 못하는 수준으로 용매의 양이 적어지면 반응 중 침전이 형성되거나 상(phase)이 역전되는 현상이 발생하게 되며, 아크릴로니트릴, 케톤류 용매가 수층에 존재하는 염기성 촉매와 직접적으로 접촉하게 되어 가수분해가 가속화되고, 상 분리가 정상적으로 일어나지 않아 수층에서부터 침전이 발생하므로 최종적으로 얻어지는 시아노에틸기를 포함하는 유기화합물에 잔존하는 아크릴로니트릴, 케톤류 용매의 부산물 함량도 높아질 수 있다. When the amount of the solvent is reduced to a level that does not dissolve all the organic compounds containing the 2-cyanoethyl group generated by the side reaction of the organic layer solvent, a precipitate is formed or a phase is reversed during the reaction. Acrylonitrile and ketone solvents come into direct contact with the basic catalyst present in the aqueous layer, accelerating hydrolysis, and phase separation does not occur normally, resulting in precipitation from the aqueous layer, resulting in organic compounds containing cyanoethyl groups. The by-product content of acrylonitrile and ketone solvents may also increase.
특히, 생성물 내에 케톤류 용매의 알돌반응으로 생성되는 하기의 화학식 1 및 화학식 2로 표기되는 부산물을 포함하고 있는 경우, 끓는점이 150℃ 이상이어서 제품의 건조시간이 오래 걸리며, 완전한 제거가 어려워 고형분의 함량이 낮아질 우려가 있다. 뿐만 아니라 건조 후에도 잔존하는 부산물로 인해 가공성이 떨어지며, 분리막 코팅 시 전해액과 부반응으로 인해 전지의 수명특성이 저하될 수 있다. In particular, when the product contains by-products represented by Chemical Formulas 1 and 2 below, which are produced by the aldol reaction of ketone solvents, the boiling point is higher than 150 ° C. There is a risk that this will decrease. In addition, processability is deteriorated due to by-products remaining after drying, and life characteristics of the battery may be deteriorated due to side reactions with the electrolyte during separator coating.
[화학식 1][Formula 1]
(상기 화학식 1에서 R1, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1~5개의 알킬기이다).(In Formula 1, R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms).
[화학식 2][Formula 2]
(상기 화학식 2에서 상기 화학식 1에서 R1, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1~5개의 알킬기이다).(In Formula 2, R 1 , R 2 and R 3 in Formula 1 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms).
따라서 본 발명의 일구현예에서는, 수산기를 갖는 유기화합물, 아크릴로니트릴, 염기성 촉매 및 케톤류 용매의 반응으로부터 형성되는 2-시아노에틸기를 포함하는 유기화합물을 생성함에 있어서, 상기 케톤류 용매의 자체 알돌반응을 감소시키기 위해 반응 조건에 있어서 상기 용매의 중량 및 상기 아크릴로니트릴의 중량 그리고 상기 반응물들과 생성되는 2-시아노에틸기를 포함하는 유기화합물의 용해도에 대한 파라미터를 조절하였다. Therefore, in one embodiment of the present invention, in producing an organic compound containing a 2-cyanoethyl group formed from the reaction of an organic compound having a hydroxyl group, acrylonitrile, a basic catalyst, and a ketone solvent, the aldol itself of the ketone solvent In order to reduce the reaction, the weight of the solvent, the weight of the acrylonitrile, and the solubility of the organic compound containing the 2-cyanoethyl group produced with the reactants were adjusted under the reaction conditions.
즉, 반응조건을 하기 수학식 1 및 수학식 2를 만족하도록 조절함으로써 반응 중 아크릴로니트릴, 케톤류 용매 등 유기층의 용매가 부반응으로 인해 소모되더라도 생성된 2-시아노에틸기를 포함하는 유기화합물이 유기층 용매에 충분히 용해되어 용액상태로 유지하도록 함으로써 고형상태의 침전물 생성을 방지할 수 있고, 결과적으로 유기층에 포함된 부산물의 함량을 최소화할 수 있다.That is, by adjusting the reaction conditions to satisfy Equations 1 and 2 below, even if the solvent of the organic layer, such as acrylonitrile and ketone solvents, is consumed due to side reactions during the reaction, the organic compound containing the 2-cyanoethyl group produced is produced in the organic layer. It is possible to prevent the formation of precipitates in a solid state by sufficiently dissolving in a solvent and maintaining the solution state, and as a result, the content of by-products included in the organic layer can be minimized.
[수학식 1][Equation 1]
[수학식 2][Equation 2]
(상기 수학식 1 및 수학식 2에서 Wa는 반응동안 생성된 2-시아노에틸기를 포함하는 유기화합물의 중량이고, Wb는 아크릴로니트릴의 중량이며, Wc는 케톤류 용매의 중량이다. 또한, 상기 수학식 1에서 Sb는 아크릴로니트릴에 대한 2-시아노에틸기를 포함하는 유기화합물의 용해도이고, Sc는 케톤류 용매에 대한 시아노에틸기를 포함하는 유기화합물의 용해도이다).(In Equations 1 and 2, Wa is the weight of an organic compound containing a 2-cyanoethyl group generated during the reaction, Wb is the weight of acrylonitrile, and Wc is the weight of a ketone solvent. In addition, the above In Equation 1, Sb is the solubility of an organic compound containing a 2-cyanoethyl group in acrylonitrile, and Sc is the solubility of an organic compound containing a cyanoethyl group in ketone solvents).
본 발명의 일 구현예에 따르면, 최종 생성물에 부반응물로 존재하는 하기 화학식 1로 표시되는 화합물과 화학식 2로 표시되는 화합물의 총량이 0.2wt%이하로 존재할 수 있다. 따라서, 순도가 높은 2-시아노에틸기를 함유하는 유기화합물의 정제과정이 보다 용이하게 진행될 수 있으며 최종 생성물의 물성이 더 향상될 수 있다.According to one embodiment of the present invention, the total amount of the compound represented by Formula 1 and the compound represented by Formula 2 present as side reactants in the final product may be 0.2 wt% or less. Therefore, the purification process of the organic compound containing a high-purity 2-cyanoethyl group can be more easily performed, and the physical properties of the final product can be further improved.
[화학식 1][Formula 1]
(상기 화학식 1에서 R1, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1~5개의 알킬기이다).(In Formula 1, R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms).
[화학식 2][Formula 2]
(상기 화학식 2에서 상기 화학식 1에서 R1, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1~5개의 알킬기이다).(In Formula 2, R 1 , R 2 and R 3 in Formula 1 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms).
상기 시아노에틸기를 포함하는 유기화합물은 시아노에틸기의 치환율이 40%이상, 더욱 바람직하게는 50%이상일 수 있다. 치환율이 40% 미만일 경우 잔존하는 수산기로 인해 물에 대한 용해성이 있어 물에 투입하여 고형화하는 과정에서 수득율이 감소할 수 있다. 또한 충분한 유전율이 발휘되지 않아 이온 전도성이 저하될 뿐만 아니라 잔존하는 수산기에 의해 전지 내에서 부반응을 일으켜 전지 성능 저하의 원인이 될 수 있다.The organic compound containing the cyanoethyl group may have a cyanoethyl group substitution rate of 40% or more, more preferably 50% or more. If the substitution rate is less than 40%, the yield may decrease during solidification by being put into water due to the solubility in water due to the remaining hydroxyl groups. In addition, ionic conductivity is lowered due to insufficient dielectric constant, and side reactions may occur in the battery due to remaining hydroxyl groups, which may cause deterioration in battery performance.
아크릴로니트릴과 아세톤 두 물질의 부반응으로 인한 감소율을 확인하기 위해 수산화나트륨 용액 (수산화나트륨 6g, 증류수 100g)에 아크릴로니트릴과 아세톤을 각각 100g 가하여 교반하면서 시간에 지남에 따라 남아있는 양(단위 g)을 구하였으며, 반응 완료 후 100℃에서 2시간 동안 진공 분위기에서 건조하여 농축시킨 잔여물의 성분을 아래 표 2에 나타내었다. 또한 시간에 대한 감소 그래프의 추세선으로부터 감소속도를 구하였다.In order to check the reduction rate due to the side reaction of the two substances, acrylonitrile and acetone, 100 g of acrylonitrile and acetone were added to a sodium hydroxide solution (6 g of sodium hydroxide, 100 g of distilled water), and the amount remaining over time (unit g) was stirred. ) was obtained, and after completion of the reaction, the components of the residue concentrated by drying in a vacuum atmosphere at 100 ° C. for 2 hours are shown in Table 2 below. In addition, the decrease rate was obtained from the trend line of the decrease graph against time.
아크릴아마이드,
소듐아크릴레이트biscyanoethyl ether,
acrylamide,
sodium acrylate
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 다만, 이는 오로지 본 발명을 예시하기 위한 것으로, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지 않는 것은 당 업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail through examples. However, this is only for exemplifying the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not to be construed as being limited by these examples.
실시예 1Example 1
폴리비닐알코올 44g을 증류수 500g에 가하고 80℃에서 용해시켜 폴리비닐알코올 용액을 제조한 후, 수산화나트륨 18g을 증류수 300g에 녹인 용액을 투입하고 교반하였다. 이어 교반을 중단하고 아크릴로니트릴 290g과 아세톤 120g을 투입하고 30℃에서 5시간 동안 교반하여 시아노에틸화 반응을 진행하였다. 반응 중 2-시아노에틸기를 포함하는 폴리비닐알코올을 충분히 용해하기 위해 아크릴로니트릴과 아세톤을 시간에 따른 부반응으로 인한 감소량에 비례하여 투입하였으며, 최종적으로 추가로 투입된 아크릴로니트릴과 아세톤의 양은 각각 120g과 80g이였다. 반응 종료 후 가해준 수산화나트륨과 같은 당량의 아세트산을 투입하여 중화한 후, 30분간 에이징하여 상분리를 유도하였다. 상부의 유기층을 증류수에 천천히 투입하여 고형화 후 아세톤에 재용해, 증류수에 재침전시키는 정제과정을 추가로 4회 반복한 후 100℃에서 진공건조하여 최종적으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다.After adding 44 g of polyvinyl alcohol to 500 g of distilled water and dissolving at 80 ° C. to prepare a polyvinyl alcohol solution, a solution in which 18 g of sodium hydroxide was dissolved in 300 g of distilled water was added and stirred. Subsequently, stirring was stopped, 290 g of acrylonitrile and 120 g of acetone were added, and the mixture was stirred at 30° C. for 5 hours to perform a cyanoethylation reaction. In order to sufficiently dissolve polyvinyl alcohol containing a 2-cyanoethyl group during the reaction, acrylonitrile and acetone were added in proportion to the amount of reduction due to side reactions over time, and finally, the amounts of additionally added acrylonitrile and acetone were respectively They were 120g and 80g. After completion of the reaction, the same amount of acetic acid as added sodium hydroxide was added to neutralize the mixture, and then aged for 30 minutes to induce phase separation. The upper organic layer was slowly added to distilled water to solidify, then re-dissolved in acetone and re-precipitated in distilled water, the purification process was repeated 4 additional times, and then vacuum-dried at 100°C to finally obtain polyvinyl alcohol containing 2-cyanoethyl group. was obtained.
실시예 2Example 2
최종적으로 추가로 투입된 아크릴로니트릴과 아세톤의 양을 180g과 120g으로 한 것을 제외하고는 실시예 1과 동일한 방법으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다.Finally, polyvinyl alcohol containing a 2-cyanoethyl group was obtained in the same manner as in Example 1, except that the amount of acrylonitrile and acetone added was changed to 180 g and 120 g.
실시예 3Example 3
최종적으로 추가로 투입된 아크릴로니트릴과 아세톤의 양을 240g과 160g으로 한 것을 제외하고는 실시예 1과 동일한 방법으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다.Finally, polyvinyl alcohol containing a 2-cyanoethyl group was obtained in the same manner as in Example 1, except that the amount of acrylonitrile and acetone added was 240 g and 160 g, respectively.
비교예 1Comparative Example 1
추가로 아크릴로니트릴과 아세톤을 가해주지 않는 것을 제외하고는 실시예1과 동일한 방법으로 진행하였다. 아세트산으로 중화한 후, 30분간 에이징하여 상분리를 유도하였다. 하부의 유기층을 증류수에 천천히 투입하여 고형화 후 아세톤에 재용해, 증류수에 재침전시키는 정제과정을 추가로 4회 반복한 후 100℃에서 진공건조하여 최종적으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다. It proceeded in the same manner as in Example 1, except that acrylonitrile and acetone were not added. After neutralization with acetic acid, phase separation was induced by aging for 30 minutes. The lower organic layer was slowly added to distilled water to solidify, then re-dissolved in acetone and re-precipitated in distilled water, the purification process was repeated 4 times, and then vacuum-dried at 100°C to finally obtain polyvinyl alcohol containing 2-cyanoethyl group. was obtained.
비교예 2Comparative Example 2
폴리비닐알코올 44g을 증류수 500g에 가하고 80℃에서 용해시켜 폴리비닐알코올 용액을 제조한 후, 수산화나트륨 18g을 증류수 300g에 녹인 용액을 투입하고 교반하였다. 이어 교반을 중단하고 아크릴로니트릴 290g을 투입하고 30℃에서 5시간 동안 교반하여 시아노에틸화 반응을 진행하였다. 반응 종료 후 가해준 수산화나트륨과 같은 당량의 아세트산을 투입하여 중화한 후, 30분간 에이징하여 상분리를 유도하였으나 고형의 침전물이 교반날에 감겨있는 상태로 존재하였다, 침전물을 교반날로부터 분리한 후 아세톤에 녹인 뒤 증류수에 재침전시키는 정제과정을 4회 반복한 후 100℃에서 진공건조하여 최종적으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다.After adding 44 g of polyvinyl alcohol to 500 g of distilled water and dissolving at 80 ° C. to prepare a polyvinyl alcohol solution, a solution in which 18 g of sodium hydroxide was dissolved in 300 g of distilled water was added and stirred. Subsequently, stirring was stopped, 290 g of acrylonitrile was added, and the mixture was stirred at 30° C. for 5 hours to perform a cyanoethylation reaction. After completion of the reaction, the same amount of acetic acid as added sodium hydroxide was added to neutralize it, and then aged for 30 minutes to induce phase separation, but a solid precipitate remained wrapped around the stirring blade. After separating the precipitate from the stirring blade, acetone After dissolving in distilled water, the purification process of reprecipitation in distilled water was repeated 4 times, and then vacuum dried at 100 ° C. to finally obtain polyvinyl alcohol containing a 2-cyanoethyl group.
비교예 3Comparative Example 3
최종적으로 추가로 투입된 아크릴로니트릴과 아세톤의 양을 240g과 0g으로 한 것을 제외하고는 실시예 1과 동일한 방법으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다.Polyvinyl alcohol containing a 2-cyanoethyl group was obtained in the same manner as in Example 1, except that the amounts of acrylonitrile and acetone that were finally added were changed to 240 g and 0 g.
비교예 4Comparative Example 4
최종적으로 추가로 투입된 아크릴로니트릴과 아세톤의 양을 180g과 0g으로 한 것을 제외하고는 실시예 1과 동일한 방법으로 진행하였다. 아세트산으로 중화한 후, 30분간 에이징하여 상분리를 유도하였으나 상분리가 이루어지지 않았으며, 생성물 용액을 과량의 증류수에 투입하여 얻은 침전물을 아세톤에 녹인 뒤 증류수에 재침전시키는 정제과정을 4회 반복한 후 100℃에서 진공건조하여 최종적으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다. It proceeded in the same manner as in Example 1, except that the amounts of acrylonitrile and acetone that were finally added were changed to 180 g and 0 g. After neutralization with acetic acid, phase separation was induced by aging for 30 minutes, but phase separation was not achieved. The product solution was added to an excess of distilled water, and the precipitate obtained was dissolved in acetone and then re-precipitated in distilled water. The purification process was repeated 4 times. After vacuum drying at 100° C., polyvinyl alcohol containing a 2-cyanoethyl group was finally obtained.
비교예 5Comparative Example 5
최종적으로 추가로 투입된 아크릴로니트릴과 아세톤의 양을 0g과 120g으로 한 것을 제외하고는 비교예1과 동일한 방법으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다.Polyvinyl alcohol containing a 2-cyanoethyl group was obtained in the same manner as in Comparative Example 1, except that the amount of acrylonitrile and acetone finally added was changed to 0 g and 120 g.
비교예 6Comparative Example 6
최종적으로 추가로 투입된 아크릴로니트릴과 아세톤의 양을 0g과 160g으로 한 것을 제외하고는 실시예 1과 동일한 방법으로 진행하였다. 아세트산으로 중화한 후, 30분간 에이징하여 상분리를 유도하였다. 하부의 유기층을 증류수에 천천히 투입하여 고형화 후 아세톤에 재용해, 증류수에 재침전시키는 정제과정을 추가로 4회 반복한 후 100℃에서 진공건조하여 최종적으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다. It proceeded in the same manner as in Example 1, except that the amount of acrylonitrile and acetone finally added was 0g and 160g. After neutralization with acetic acid, phase separation was induced by aging for 30 minutes. The lower organic layer was slowly added to distilled water to solidify, then re-dissolved in acetone and re-precipitated in distilled water, the purification process was repeated 4 times, and then vacuum-dried at 100°C to finally obtain polyvinyl alcohol containing 2-cyanoethyl group. was obtained.
비교예 7Comparative Example 7
최종적으로 추가로 투입된 아크릴로니트릴과 아세톤의 양을 30g과 20g으로 한 것을 제외하고는 비교예4과 동일한 방법으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다.Finally, polyvinyl alcohol containing a 2-cyanoethyl group was obtained in the same manner as in Comparative Example 4, except that the amount of acrylonitrile and acetone added was changed to 30 g and 20 g.
비교예 8Comparative Example 8
폴리비닐알코올 44g을 증류수 500g에 가하고 80℃에서 용해시켜 폴리비닐알코올 용액을 제조한 후, 수산화나트륨 18g을 증류수 300g에 녹인 용액을 투입하고 교반하였다. 이어 교반을 중단하고 아크릴로니트릴 470g과 아세톤 120g을 투입하고 30℃에서 5시간 동안 교반하여 시아노에틸화 반응을 진행하였다. 반응 중 2-시아노에틸기를 포함하는 폴리비닐알코올을 충분히 용해하기 위해 아세톤을 시간에 따른 부반응으로 인한 감소량에 비례하여 투입하였으며, 최종적으로 추가로 투입된 아세톤의 양은 120g이였다. 반응 종료 후 가해준 수산화나트륨과 같은 당량의 아세트산을 투입하여 중화한 후, 30분간 에이징하여 상분리를 유도하였으나 상분리가 이루어지지 않았으며, 생성물 용액을 과량의 증류수에 투입하여 얻은 침전물을 아세톤에 녹인 뒤 증류수에 재침전시키는 정제과정을 4회 반복한 후 100℃에서 진공건조하여 최종적으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다. After adding 44 g of polyvinyl alcohol to 500 g of distilled water and dissolving at 80 ° C. to prepare a polyvinyl alcohol solution, a solution in which 18 g of sodium hydroxide was dissolved in 300 g of distilled water was added and stirred. Subsequently, stirring was stopped, 470 g of acrylonitrile and 120 g of acetone were added, and the mixture was stirred at 30° C. for 5 hours to perform a cyanoethylation reaction. In order to sufficiently dissolve polyvinyl alcohol containing a 2-cyanoethyl group during the reaction, acetone was added in proportion to the decrease due to the side reaction over time, and the amount of acetone additionally added was 120 g. After completion of the reaction, the same amount of acetic acid as added sodium hydroxide was added to neutralize it, and then aged for 30 minutes to induce phase separation, but phase separation was not achieved. After repeating the purification process of re-precipitation in distilled water 4 times, vacuum drying was performed at 100° C. to finally obtain polyvinyl alcohol containing a 2-cyanoethyl group.
비교예 9Comparative Example 9
폴리비닐알코올 44g을 증류수 500g에 가하고 80℃에서 용해시켜 폴리비닐알코올 용액을 제조한 후, 수산화나트륨 18g을 증류수 300g에 녹인 용액을 투입하고 교반하였다. 이어 교반을 중단하고 아크릴로니트릴 290g과 아세톤 240g을 투입하고 30℃에서 5시간 동안 교반하여 시아노에틸화 반응을 진행하였다. 반응 중 2-시아노에틸기를 포함하는 폴리비닐알코올을 충분히 용해하기 위해 아크릴로니트릴을 시간에 따른 부반응으로 인한 감소량에 비례하여 투입하였으며, 최종적으로 추가로 투입된 아크릴로니트릴의 양은 180g이였다. 반응 종료 후 가해준 수산화나트륨과 같은 당량의 아세트산을 투입하여 중화한 후, 30분간 에이징하여 상분리를 유도하였다. 아세트산으로 중화한 후, 30분간 에이징하여 상분리를 유도하였다. 하부의 유기층을 증류수에 천천히 투입하여 고형화 후 아세톤에 재용해, 증류수에 재침전시키는 정제과정을 추가로 4회 반복한 후 100℃에서 진공건조하여 최종적으로 2-시아노에틸기를 포함하는 폴리비닐알코올을 수득하였다. After adding 44 g of polyvinyl alcohol to 500 g of distilled water and dissolving at 80 ° C. to prepare a polyvinyl alcohol solution, a solution in which 18 g of sodium hydroxide was dissolved in 300 g of distilled water was added and stirred. Subsequently, stirring was stopped, 290 g of acrylonitrile and 240 g of acetone were added, and the mixture was stirred at 30° C. for 5 hours to perform a cyanoethylation reaction. In order to sufficiently dissolve polyvinyl alcohol containing a 2-cyanoethyl group during the reaction, acrylonitrile was added in proportion to the decrease due to the side reaction over time, and finally, the amount of acrylonitrile additionally added was 180 g. After completion of the reaction, the same amount of acetic acid as added sodium hydroxide was added to neutralize the mixture, and then aged for 30 minutes to induce phase separation. After neutralization with acetic acid, phase separation was induced by aging for 30 minutes. The lower organic layer was slowly added to distilled water to solidify, then redissolved in acetone and then re-precipitated in distilled water, the purification process was repeated 4 times, and then vacuum-dried at 100°C to finally obtain polyvinyl alcohol containing 2-cyanoethyl group. was obtained.
시아노에틸기의 치환율 계산Calculation of substitution rate of cyanoethyl group
실시예 및 비교예에서 얻어진 시아노에틸기를 포함하는 유기화합물의 치환율은 Kjeldahl method를 이용하여 질소 정량분석을 한 후 수산기를 포함하는 유기화합물의 반복단위와 시아노에틸기를 포함하는 유기화합물의 반복단위의 분자량으로부터 질소 함량에 대한 계산식을 통해 산출하였다. 상세하게는 시아노에틸기를 포함하는 유기화합물을 소수점 네 번째 자리까지 정확히 측량하고 98% 진한 황산과 분해촉진제를 가해 완전한 용액상태가 될 때까지 가열하였다. 제조된 용액은 상온까지 완전히 식힌 후 물과 32% 수산화나트륨 용액을 가하여 염기성으로 전환한 후 증기에 포함되어 나오는 암모니아성 질소를 지시약을 포함하는 붕산용액에 흡수시켰다. 다음으로 0.1N 염산 표준용액으로 기존 붕산용액의 파장에 도달할 때까지 적정하여 질소함량을 구한 후 계산식에 대입하여 치환율을 산출하였다. The substitution rate of the organic compound containing a cyanoethyl group obtained in Examples and Comparative Examples was determined by nitrogen quantitative analysis using the Kjeldahl method, and then the repeating unit of the organic compound containing a hydroxyl group and the repeating unit of the organic compound containing a cyanoethyl group It was calculated from the molecular weight of through a formula for nitrogen content. Specifically, an organic compound containing a cyanoethyl group was measured accurately to the fourth decimal place, and 98% concentrated sulfuric acid and a decomposition promoter were added and heated until a complete solution was obtained. The prepared solution was cooled completely to room temperature, converted to basic by adding water and 32% sodium hydroxide solution, and absorbed ammonia nitrogen contained in the vapor into boric acid solution containing an indicator. Next, titration was performed with 0.1N hydrochloric acid standard solution until the wavelength of the existing boric acid solution was reached to obtain the nitrogen content, and then the substitution rate was calculated by substituting it into the calculation formula.
불순물 확인Impurity check
실시예 및 비교예에서 얻어진 시아노에틸기를 포함하는 유기화합물을 GC-FID(기기명 : GC-2010, 제조사 : Shimadzu) 및 FT-IR (기기명 : NICOLET iS20; 제조사 : thermo scientific)을 통해 스펙트럼을 얻은 후 디아세톤 알코올, 아크릴아마이드 및 아크릴산/소듐아크릴레이트의 피크 존재 유/무를 확인하고 정량분석을 통해 시아노에틸기를 포함하는 유기화합물에 포함되어 있는 함량을 산출하였다. Spectra were obtained through GC-FID (device name: GC-2010, manufacturer: Shimadzu) and FT-IR (device name: NICOLET iS20; manufacturer: thermo scientific) for organic compounds containing cyanoethyl groups obtained in Examples and Comparative Examples After confirming the presence/absence of peaks of diacetone alcohol, acrylamide, and acrylic acid/sodium acrylate, the content contained in the organic compound containing a cyanoethyl group was calculated through quantitative analysis.
또한, 해당하는 피크가 시아노에틸기를 함유하는 유기화합물과 화학적으로 결합되어 있는 작용기에 의한 것인지 확인하기 위하여 상기 피크를 포함하는 시아노에틸기를 포함하는 유기화합물에 대해 아세톤에 재용해시킨 후 물에 투입하여 고형화하는 정제과정을 3회 추가로 진행한 후 건조하여 FT-IR 스펙트럼을 다시 얻은 후 피크 변화를 확인하였으며, 그 결과를 아래 표3 에 나타내었다.In addition, in order to confirm that the corresponding peak is due to a functional group chemically bonded to the organic compound containing a cyanoethyl group, the organic compound containing the cyanoethyl group including the peak was re-dissolved in acetone and then dissolved in water. The purification process of adding and solidifying was additionally carried out three times, and then dried to obtain an FT-IR spectrum again, and the peak change was confirmed. The results are shown in Table 3 below.
수득률 계산yield calculation
실시예 및 비교예에서 가해준 수산기를 포함하는 유기화합물의 양과 얻어진 시아노에틸기를 포함하는 유기화합물의 치환율로부터 몰분율 및 단량체 분자량을 이용하여 이론적 수득량을 계산하고 실제로 얻어진 시아노에틸기를 포함하는 유기화합물의 양과 비교해 수득률을 산출하였다.The theoretical yield was calculated using the mole fraction and monomer molecular weight from the amount of the organic compound containing a hydroxyl group added in Examples and Comparative Examples and the substitution rate of the obtained organic compound containing a cyanoethyl group, and the organic containing cyanoethyl group actually obtained The yield was calculated by comparing the amount of compound.
가해준
아크릴로니트릴의 양 (g)first
perpetrated
Amount of acrylonitrile (g)
가해준
아세톤의
양(g)first
perpetrated
of acetone
Amount (g)
아크릴로니트릴의 양(g)added
Amount of acrylonitrile (g)
아세톤의 양
(g)added
amount of acetone
(g)
(유기층)phase separation
(organic layer)
(%)substitution rate
(%)
(%)yield
(%)
(wt%)*diacetone alcohol
(wt%)*
실시예 1 내지 3에서 반응 종료 후 시아노에틸기를 포함하는 폴리비닐알코올은 높은 치환율과 함께 유기층이 상부에 안정적으로 형성되어 정제과정에서 발생하는 손실이 없으므로 높은 수득률을 얻을 수 있었다. 또한 최종적으로 얻어진 제품에 포함되어 있는 아세톤의 부반응으로부터 생성되는 디아세톤 알코올이 검출되지 않았다. After completion of the reaction in Examples 1 to 3, polyvinyl alcohol containing a cyanoethyl group had a high substitution rate and an organic layer was stably formed on the top, so that a high yield was obtained because there was no loss during the purification process. Also, diacetone alcohol produced from a side reaction of acetone contained in the finally obtained product was not detected.
한편, 비교예1, 비교예6, 비교예9의 경우 반응 종료 후 유기층 내 시아노에틸기를 포함하는 폴리비닐알코올의 농도가 높아 유기층이 하부에 형성되었으며, 치환율과 수득률이 낮았다. 또한 최종 제품에 포함되어 있는 디아세톤 알코올이 검출됨을 확인하였다. 비교예2에서는 반응 전 또는 반응 중에 아세톤을 포함하지 않았으며, 정제과정에서만 아세톤이 사용된 경우로, 최종 제품에 디아세톤 알코올의 검출되지 않았다. 비교예2, 비교예5에서는 공통적으로 생성된 시아노에틸기를 포함하는 폴리비닐알코올을 모두 용해시킬 수 있는 양보다 적은 유기층의 용매로 인해 반응이 종결되기 전에 작은 입자가 보이기 시작했으며, 점차 입자의 크기가 커지다가 교반날에 감기는 로드클라이밍 현상이 발생하였다.On the other hand, in the case of Comparative Example 1, Comparative Example 6, and Comparative Example 9, after completion of the reaction, the organic layer was formed at the bottom due to the high concentration of polyvinyl alcohol containing a cyanoethyl group in the organic layer, and the substitution rate and yield were low. In addition, it was confirmed that diacetone alcohol contained in the final product was detected. In Comparative Example 2, acetone was not included before or during the reaction, and acetone was used only in the purification process, and diacetone alcohol was not detected in the final product. In Comparative Examples 2 and 5, small particles began to appear before the reaction was terminated due to the amount of solvent in the organic layer less than the amount capable of dissolving all of the commonly produced polyvinyl alcohol containing a cyanoethyl group. As the size increased, a rod climbing phenomenon occurred that was wound around the stirring blade.
비교예 4, 비교예7, 비교예8에서는 반응 종료 후 시아노에틸기를 포함하는 폴리비닐알코올을 포함하는 유기층이 형성되지 않고 용액 내에서 분산된 상태로 얻어졌으며, 생성용액 전체를 과량의 증류수에 투입하여 고형화하였다. 이로 인해 고형화 과정에서 과량의 손실이 발생하였으며, 반응 중 수층에 존재하던 디아세톤 알코올이 다량 검출되었다.In Comparative Example 4, Comparative Example 7, and Comparative Example 8, after completion of the reaction, an organic layer containing polyvinyl alcohol containing a cyanoethyl group was not formed and was obtained in a dispersed state in the solution. It was added and solidified. As a result, excessive loss occurred during the solidification process, and a large amount of diacetone alcohol present in the aqueous layer was detected during the reaction.
Claims (10)
상기 반응 과정에 있어서 2-시아노에틸기를 포함하는 유기화합물에 대한 아크릴로니트릴의 중량 및 케톤류 용매의 중량과 상기 유기화합물에 대한 상기 아크릴로니트릴 및 케톤류 용매의 용해도의 관계가 하기의 수학식 1을 만족하도록 반응조건을 설정하는 것인, 2-시아노에틸기를 포함하는 유기화합물의 제조방법:
[수학식 1]
[수학식 2]
(상기 수학식 1 및 수학식 2에서 Wa는 반응동안 생성된 2-시아노에틸기를 포함하는 유기화합물의 중량이고, Wb는 아크릴로니트릴의 중량이며, Wc는 케톤류 용매의 중량이다. 또한, 상기 수학식 1에서 Sb는 아크릴로니트릴에 대한 2-시아노에틸기를 포함하는 유기화합물의 용해도이고, Sc는 케톤류 용매에 대한 시아노에틸기를 포함하는 유기화합물의 용해도이다).A method for producing an organic compound containing a 2-cyanoethyl group formed by the reaction of a hydroxyl group-containing organic compound, acrylonitrile, a basic catalyst and a ketone solvent,
In the reaction process, the relationship between the weight of acrylonitrile and the weight of ketone solvents for the organic compound containing a 2-cyanoethyl group and the solubility of the acrylonitrile and ketone solvents for the organic compound is expressed by Equation 1 below: Method for producing an organic compound containing a 2-cyanoethyl group, wherein the reaction conditions are set to satisfy:
[Equation 1]
[Equation 2]
(In Equations 1 and 2, Wa is the weight of an organic compound containing a 2-cyanoethyl group generated during the reaction, Wb is the weight of acrylonitrile, and Wc is the weight of a ketone solvent. In addition, the above In Equation 1, Sb is the solubility of an organic compound containing a 2-cyanoethyl group in acrylonitrile, and Sc is the solubility of an organic compound containing a cyanoethyl group in ketone solvents).
[화학식 1]
(상기 화학식 1에서 R1, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1~5개의 알킬기이다), 및
[화학식 2]
(상기 화학식 2에서 상기 화학식 1에서 R1, R2 및 R3는 각각 독립적으로 수소 또는 탄소수 1~5개의 알킬기이다).In the organic compound containing a 2-cyanoethyl group formed by the reaction of a hydroxyl group-containing organic compound, acrylonitrile, a basic catalyst and a ketone solvent, the organic compound containing the 2-cyanoethyl group is represented by the following formula (1) An organic compound containing a 2-cyanoethyl group, wherein the total amount of the compound and the compound represented by Formula 2 below is 0.2 wt% or less relative to the total amount of the organic compound containing the 2-cyanoethyl group:
[Formula 1]
(In Formula 1, R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms), and
[Formula 2]
(In Formula 2, R 1 , R 2 and R 3 in Formula 1 are each independently hydrogen or an alkyl group having 1 to 5 carbon atoms).
The organic compound containing a 2-cyanoethyl group according to claim 6, wherein the hydroxyl group-containing organic compound includes polyvinyl alcohol.
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